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Title:
METHODS FOR PREPARING ETHERS, HALOGENATED ETHERS, FLUOROETHERS AS WELL AS USES OF THE LATTER IN FIRE EXTINGUISHING SYSTEMS.
Document Type and Number:
WIPO Patent Application WO/2004/018553
Kind Code:
A2
Abstract:
Highly fluorinated, saturated, and unsaturated fluoroethers are efficient, economical, non-ozone-depleting fire extinguishing agents used alone or in blends with other fire extinguishing agents in total flooding and portable systems. Methods for producing ethers, halogenated ether intermediates, and fluoroethers are disclosed. Novel fluoroether compositions are disclosed. Fluoroether extinguishing mixtures, methods, and systems are disclosed.

Inventors:
CHIEN JOHN PH D (US)
ROWLAND THOMAS F (US)
ROBIN MARK L PH D (US)
BOGGS JANET (US)
COHN MITCHEL PH D (US)
HEDRICK VICKI (US)
BRANDSTADTER STEPHAN PH D
Application Number:
PCT/US2003/019693
Publication Date:
March 04, 2004
Filing Date:
June 19, 2003
Export Citation:
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Assignee:
PCBU SERVICES INC (US)
CHIEN JOHN PH D (US)
ROWLAND THOMAS F (US)
ROBIN MARK L PH D (US)
BOGGS JANET (US)
COHN MITCHEL PH D (US)
International Classes:
A62D1/00; A62D1/08; C07C41/06; C07C41/22; C07C43/12; (IPC1-7): C08L/
Foreign References:
US2975163A1961-03-14
US2671799A1954-03-09
US6416683B12002-07-09
GB1571356A1980-07-16
US3943256A1976-03-09
US4014799A
Other References:
A. L. HENNE ET AL.: "Fluorinated ethers" J.AM.CHEM.SOC., vol. 72, 1972, pages 4378-4380, XP002277286
V.A. GUBANOV ET AL.: 'Reaction of hexafluoropropene with (perfluorooalkyl)methanols' J. GEN. CHEM. vol. 35, 1965, pages 399 - 400, XP009029609
DATABASE CROSSFIRE BEILSTEIN BEILSTEIN INSTITUT ZUR FÖRDERUNG DER CHEMISCHEN WISSENSCHAFTEN; XP002277291 Database accession no. 5257400 & V. A. PETROV ET AL.: J. FLUORINE CHEM., vol. 95, no. 1, 1999, pages 5-14, XP009029645
R.C. TERRELL ET AL.: "General anesthetics. 1. Halogenated methyl ethyl ethers as anesthetic agents." JOURNAL OF MEDICINAL CHEMISTRY, vol. 14, no. 6, 1971, pages 517-519, XP002287171
J.D.PARK ET AL.: "Directed chlorination of fluorinated aliphatic ethers." JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 74, 1952, pages 2292-2294, XP002287172
R.C.TERRELL ET AL.: "General anesthetics. 3. Fluorinated methyl ethyl ethers as anesthetic agents." JOURNAL OF MEDICINAL CHEMISTRY, vol. 15, no. 6, 1972, pages 604-606, XP002287173
K. K. JOHRI ET AL.: "Comparison of the reactivity of CF3OX (X = Cl, F) with some simple alkenes." JOURNAL OF ORGANIC CHEMISTRY, vol. 48, 1983, pages 242-250, XP000881790
V.A. PETROV: "New synthesis of hydrofluoroethers." JOURNAL OF FLUORINE CHEMISTRY, vol. 112, 2001, pages 117-121, XP004322994
B.B.RANDOLPH ET AL.: "Synthesis of functionalized polyfluoroalkyl hypochlorites and fluoroxy compounds and their reactions with some fluoroalkenes." JOURNAL OF FLUORINE CHEMISTRY, vol. 64, 1993, pages 129-149, XP002287174
DATABASE BEILSTEIN BEILSTEIN INSTITUTE FOR ORGANIC CHEMISTRY, FRANKFURT-MAIN, DE; XP002287175 Database accession no. 8203460 & T.A. BISPEN ET AL.: JOURNAL OF APPLIED CHEMISTRY, vol. 71, no. 6, 1998, pages 1009-1013,
DATABASE BEILSTEIN BEILSTEIN INSTITUTE FOR ORGANIC CHEMISTRY, FRANKFURT-MAIN, DE; XP002287176 Database accession no. 2642703 & V.V.BERENBLIT ET AL.: JOURNAL OF ORGANIC CHEMISTRY USSR, vol. 12, 1976, pages 765-768,
DATABASE BEILSTEIN BEILSTEIN INSTITUTE FOR ORGANIC CHEMISTRY, FRANKFURT-MAIN, DE; XP002287177 Database accession no. 4744596 & S.D. CHEPIK ET AL.: BULL.ACAD.SCI.USSR DIV.CHEM.SCI., vol. 40, no. 8.2, 1991, pages 1712-1714,
DATABASE BEILSTEIN BEILSTEIN INSTITUTE FOR ORGANIC CHEMISTRY, FRANKFURT-MAIN, DE; XP002287178 Database accession no. 5429529 & S.D.CHEPIK ET AL.: BULL.ACAD.SCI.USSR DIV.CHEM.SCI., vol. 40, no. 8.2, 1991, pages 1712-1714,
DATABASE BEILSTEIN BEILSTEIN INSTITUTE FOR ORGANIC CHEMISTRY, FRANKFURT-MAIN, DE; XP002287179 Database accession no. 2454312 & V.S. YUMINOV ET AL.: J.GEN.CHEM.USSR, vol. 37, 1967, pages 350-354,
DATABASE BEILSTEIN BEILSTEIN INSTITUTE FOR ORGANIC CHEMISTRY, FRANKFURT-MAIN, DE; XP002287180 Database accession no. 1856325 & V.V.BERENBLIT ET AL.: JOURNAL OF ORGANIC CHEMISTRY USSR, vol. 12, 1976, pages 765-768,
Attorney, Agent or Firm:
Hyta, Robert C. (P.S. 601 W. First Avenue, Suite 130, Spokane WA, US)
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Claims:
CLAIMS The invention claimed is:
1. A method for preparing an ether comprising: mixing a basic aqueous solution with an alcohol to form a first reactant mixture; providing an olefin having the general formula R' (R2) C=CXY, wherein the R1 group is selected from the group comprising hydrogens, halogens, halogenated alkyl groups, hydrogenated alkyl groups or perhalogenated alkyl groups, R2 is selected from the group comprising hydrogens, halogens, halogenated alkyl groups, hydrogenated alkyl groups or perhalogenated alkyl groups, X and Y are selected from the group comprising H, I, Br, Cl, or F, and X and Y can be the same as one another or different; and combining the first reactant mixture with the olefin to form an ether having the general formula R3CXY0R4, wherein the R3 group is selected from the group comprising hydrogenated alkyl groups, halogenated alkyl groups, or perhalogenated alkyl groups and the R4 group is selected from the group comprising hydrogenated alkyl groups, halogenated alkyl groups, or perhalogenated alkyl groups.
2. The method of claim 1, wherein the basic aqueous solution comprises from about 10 % (wt. /wt.) to about 45% (wt./wt.) KOH.
3. The method of claim 1, wherein the first reactant mixture comprises from about 50 % (wt. /wt.) to about 60% (wt./wt.) alcohol.
4. The method of claim 1, wherein the R'group is selected from the group comprising CF3or F.
5. The method of claim 1, wherein the R2 group is selected from the group comprising H or F.
6. The method of claim 1, wherein the R'group is selected from the group comprising CF3or F and the R2 group is selected from the group comprising H or F.
7. The method of claim 1, wherein the X is the same element as the Y.
8. The method of claim 1, wherein the X is selected from the group comprising F or H and the Y is selected from the group comprising F or H.
9. The method of claim 1, wherein the olefin is selected from the group comprising CF3CF=CF2, CF3CH=CF2, or CF2=CF2.
10. The method of claim 1, wherein the olefin comprises CF3CF=CF2.
11. The method of claim 1, wherein the olefin comprises CF2=CF2.
12. The method of claim 1, wherein the combining is performed in a reaction vessel having a temperature from about10°C to about 50°C.
13. The method of claim 1, wherein the R3 group is selected from the group comprising CF3CHF, CF3CH2, or CHF2.
14. The method of claim 1, wherein the R3 group comprises CF3CHF.
15. The method of claim 1, wherein the R3 group comprises CHF2.
16. The method of claim 1, wherein the R4 group is selected from the group comprisingCH3,CH2CH3 orCH (CH3) 2.
17. The method of claim 1, wherein the R4 group comprisesCH3.
18. The method of claim 1, wherein the ether comprises CF3CHFCF20CH3.
19. The method of claim 1, wherein the ether comprises CHF2CF20CH3.
20. The method of claim 1, wherein the ether comprises CF3CH2CF20CH3.
21. The method of claim 1, further comprising separating the ether from the olefin and alcohol by removing the ether in liquid form.
22. The method of claim 1, wherein the preparation of the ether further includes the formation of at least two layers, a bottom layer comprising the ether and an upper layer comprising an aqueous solution.
23. The method of claim 22, wherein the first reactant mixture comprises the upper layer.
24. A method for preparing halogenated ether intermediates comprising: providing a photochemical reactor containing an ether having the general formula R3CXY0R4, wherein the R3 group is selected from the group comprising hydrogenated alkyl groups, halogenated alkyl groups, or perhalogenated alkyl groups and the R4 group is selected from the group comprising hydrogenated alkyl groups, halogenated alkyl groups, or perhalogenated alkyl groups, X and Y are selected from the group comprising H, I, Br, Cl, or F, and X and Y can be the same as one another or different; and reacting the ether with a gaseous halogenating agent in the presence of actinic energy to produce a halogenated ether intermediate having the general formula CXY0R, wherein the R5 group is selected from the group comprising halogenated alkyl groups, or perhalogenated alkyl groups and the R6 group is selected from the group comprising halogenated alkyl groups, or perhalogenated alkyl groups.
25. The method of claim 24, wherein the R3 group is selected from the group comprising CF3CHF, CF3CH2, or CHF2.
26. The method of claim 24, wherein the R3 group comprises CF3CHF.
27. The method of claim 24, wherein the R3 group comprises CHF2.
28. The method of claim 24, wherein the~R4 group is selectedfrom the group comprisingCH3,CH2CH3 orCH (CH3) 2.
29. The method of claim 24, wherein the R4 group comprisesCH3.
30. The method of claim 24, wherein the ether comprises CF3CHFCF20CH3.
31. The method of claim 24, wherein the ether comprises CHF2CF20CH3.
32. The method of claim 24, wherein the ether comprises CF3CH2CF20CH3.
33. The method of claim 24, wherein the X is the same element as the Y.
34. Docket No. PC3045.
35. The method of claim 24, wherein the X is selected from the group comprising F or H and the Y is selected from the group comprising F or H.
36. The method of claim 24, wherein the actinic energy comprises uv radiation.
37. The method of claim 24, wherein the gaseous halogenating agent comprises chlorine.
38. The method of claim 24, wherein the reacting occurs at a temperature from about 10°C to about 70°C.
39. The method of claim 24, wherein the R5 group is selected from the group comprising CF3CHF, CF3CCIF, CF3CH2, CF3CHCI, CF3CC12, CHF2or CCIF2.
40. The method of claim 24, wherein the R5 group comprises CF3CHF.
41. The method of claim 24, wherein the R5 group comprises CHF2.
42. The method of claim 24, wherein the R6 group is selected from the group comprisingCH2CI,CHCh, or CCl3.
43. The method of claim 24, wherein the R6 group comprisesCHCI2.
44. The method of claim 24, wherein the R6 group comprisesCCI3.
45. The methodofclaim 24, wherein the halogenated ether intermediate comprises CF3CHFCF20CCI3.
46. The method of claim 24, wherein the halogenated ether intermediate comprises CF3CHFCF20CHC12.
47. The method of claim 24, wherein the halogenated ether intermediate comprises CF3CClFCF2OCCl3.
48. The method of claim 24, wherein the halogenated ether intermediate comprises CF3CHFCF2OCH2Cl.
49. Docket No. PC3045.
50. The method of claim 24, wherein the halogenated ether intermediate comprises CCIF2CF20CCI3.
51. The method of claim 24, wherein the halogenated ether intermediate comprises CFsCH2CF20CCi3.
52. A method for preparing fluoroethers comprising: providing a halogenated ether intermediate comprising R5CXYOR6, wherein the R5 group is selected from the group comprising hydrogenated alkyl groups, halogenated alkyl groups, or perhalogenated alkyl groups and the R6 group is selected from the group comprising halogenated alkyl groups or perhalogenated alkyl groups, X and Y are selected from the group comprising H, I, Br, Ci, or F, and X and Y can be the same as one another or different, wherein the halogenated ether intermediate includes at least one halogen selected from the group comprising 1, Br, or Cl ; fluorinating the halogenated ether intermediate in the presence of HF and a catalyst to produce a fluoroether comprising R'OR8, wherein the R7 group is selected from the group comprising hydrogenated alkyl groups, hydrofluorohalogenated alkyl groups, hydrofluorinated alkyl groups, fluorohalogenated alkyl groups, or perfluorinated alkyl groups and R3 is selected from the group comprising hydrofluorohalogenated alkyl groups, hydrofluorinated alkyl groups, fluorohalogenated alkyl groups, or perfluorinated alkyl groups.
53. The method of claim 50, wherein the R5 group is selected from the group comprising CF3CHF, CF3CCIF,CF3CH2, CF3CHCI, CF3CCI2, CHF2, or CCIF2.
54. The method of claim 50, wherein the R5 group comprises CF3CHF.
55. The method of claim 50, wherein the R5 group comprises CHF2.
56. The method of claim 50, wherein the R6 group is selected from the group comprisingCH2CI,CHC12, orCCI3.
57. The method of claim 50, wherein the R6 group comprisesCHCi2.
58. The method of claim 50, wherein the R6 group comprisesCCI3.
59. Docket No. PC3045.
60. The method of claim 50, wherein the halogenated ether intermediate comprises CF3CHFCF2OCCI3.
61. The method of claim 50, wherein the halogenated ether intermediate comprises CF3CHFCF20CHC12.
62. The method of claim 50, wherein the halogenated ether intermediate comprises CF3CHFCF20CH2CI.
63. The method of claim 50, wherein the halogenated ether intermediate comprises CF3CCIFCF20CC13.
64. The method of claim 50, wherein the halogenated ether intermediate comprises CCIF2CF20CCI3.
65. The method of claim 50, wherein the halogenated ether intermediate comprises CF3CCI2CF20CCI3.
66. The method of claim 50, wherein the X is the same element as the Y.
67. The method of claim 50, wherein the X is selected from the group comprising F or H and the Y is selected from the group comprising F or H.
68. The method of claim 50, wherein the HF is in gas form.
69. The method of claim 50, wherein the fluorination occurs at a temperature of from about 100°C to about 300°C.
70. The method of claim 50, wherein the catalyst comprises chromium.
71. The method of claim 50, wherein the catalyst comprises activated carbon.
72. The method of claim 50, wherein R7 is selected from the group comprising CF3CHFCF2, CF3CCIFCF2, CF3CF2CF2, CF3CH2CF2, CF3CHCICF2, CF3CCI2CF2, CHF2CF2, CF3CF2, or CCIF2CF2.
73. The method of claim 50, wherein R 7comprises CF3CHFCF2.
74. Docket No. PC3045.
75. The method of claim 50, wherein R8 is selected from the group comprisingCFCI2,CF2CI,CF3,CHFCI,CF2H, orCFH2.
76. The method of claim 50, wherein the fluoroether comprises CF3CHFCF20CF3.
77. The method of claim 50, wherein the fluoroether comprises CF3CHFCF20CHF2.
78. The method of claim 50, wherein the fluoroether comprises CF3CF2CF20CF3.
79. A method for the preparation of fluoroethers comprising: providing an ether having at least one halogen selected from the group comprising 1, Br, or Cl ; and fluorinating the ether in the presence of liquid HF at a first temperature to produce a first fluoroether having at least one more fluorine atom than the ether.
80. The method of claim 75 wherein the ether comprises the general formula R5CXYOR6, wherein the R5 group is selected from the group comprising hydrogenated alkyl groups, halogenated alkyl groups, or perhalogenated alkyl groups and the R6 group is selected from the group comprising hydrogenated alkyl groups, halogenated alkyl groups, or perhalogenated alkyl groups, X and Y are selected from the group comprising H, I, Br, Cl, or F, and X and Y can be the same as one another or different, wherein the halogenated ether intermediate includes at least one halogen selected from the group comprising 1, Br, or Cl.
81. The method of claim 75, wherein the R5 group is selected from the group comprising CF3CHF, CF3CCIF, CF3CH2, CF3CHCI, CF3CC12, CHF2, or CCIF2.
82. The method of claim 75, wherein the R5 group comprises CF3CHF.
83. The method of claim 75, wherein the R5 group comprises CHF2.
84. The method of claim 75, wherein the R6 group is selected from the group comprisingCH2CI,CHC12, orCCI3.
85. The method of claim 75, wherein the R6 group comprisesCHCI2.
86. The method of claim 75, wherein the R6 group comprisesCCI3.
87. The method of claim 75, wherein the ether comprises CF3CHFCF20CC13.
88. The method of claim 75, wherein the ether comprises CF3CHFCF20CHC12.
89. The method of claim 75, wherein the ether comprises CF3CHFCF20CH2CI.
90. The method of claim 75, wherein the ether comprises CF3CCIFCF20CCI3.
91. The method of claim 75, wherein the ether comprises CCIF2CF20CCI3.
92. The method of claim 75, wherein the ether comprises CF3CH2CF2OCCl3.
93. The method of claim 75, wherein the X is the same element as the Y.
94. The method of claim 75, wherein the X is selected from the group comprising F or H and the Y is selected from the group comprising F or H.
95. The method of claim 75, wherein the first temperature is from about 40°C to about 120°C.
96. The method of claim 75, wherein the first fluoroether is selected from the group comprising CF3CHFCF20CFC12, CF3CHFCF20CF2CI, CHF2CF20CFC12, or CHF2CF20CF2CI.
97. The method of claim 75, further comprising fluorinating the first fluoroether in the presence of HF at a second temperature to produce a second fluoroether comprising R7oR8, wherein the R7 group is selected from the group comprising hydrogenated alkyl groups, hydrofluorohalogenated alkyl groups, hydrofluorinated alkyl groups, fluorohalogenated alkyl groups or perfluorinated alkyl groups and R8 is selected from the group comprising hydrofluorohalogenated alkyl groups, hydrofluorinated alkyl groups, fluorohalogenated alkyl groups or perfluorinated alkyl groups.
98. Docket No. PC3045.
99. The method of claim 93 wherein the first temperature is lower than the second temperature.
100. The method of claim 93, wherein the first temperature is from about 40°C to about 120°C and the second temperature is from about 100°C to about 300°C.
101. The method of claim 93, wherein the fluorinating of the first fluoroether occurs in the presence of a catalyst.
102. The method of claim 96, wherein the catalyst comprises chromium.
103. The method of claim 96, wherein the catalyst comprises activated carbon.
104. The method of claim 96, wherein the fluorination or the first fluoroether occurs in the presence of gaseous HF.
105. The method of claim 93, wherein R7 is selected from the group comprising CF3CHFCF2, CF3CCIFCF2, CF3CF2CF2, CF3CH2CF2, CF3CHCICF2, CF3CCI2CF2, CHF2CF2, CF3CF2, or CCIF2CF2.
106. The method of claim 93, wherein R7 comprises CF3CHFCF2.
107. The method of claim 93, wherein R8 is selected from the group comprisingCFC12,CF2CI,CF3,CHFCI,CF2H, orCFH2.
108. The method of claim 93, wherein the second fluoroether comprises CF3CHFCF20CF3.
109. The method of claim 93, wherein the second fluoroether comprises CF3CHFCF20CHF2.
110. The method of claim 93, wherein the second fluoroether comprises CF3CF2CF20CF3.
111. The method of claim 93, wherein the second fluoroether comprises CHF2CF20CF3. Docket No. PC3045 107.
112. The method of claim 93, wherein the second fluoroether comprises CHF2CF20CHF2.
113. A method for manufacturing fluoroethers comprising: combining an alcohol with an olefin to produce an ether; reacting the ether with a halogenating agent to produce a halogenated ether intermediate; and fluorinating the halogenated ether intermediate with HF to form a fluoroether.
114. A method for manufacturing fluoroethers comprising: combining an alcohol with an olefin to produce an ether; reacting the ether with a halogenating agent to produce a halogenated ether intermediate; in the first instance, fluorinating the halogenated ether intermediate with HF at a first temperature to form a fluoroether intermediate; and in the second instance, fluorinating the fluoroether intermediate with HF at a second temperature to form a fluoroether.
115. A mixture within a space comprising an extinguishing compound having the general formula Z1 o z2, wherein Z'is selected from the group comprising CF3CHFCF2, CF3CF2CF2, (CF3) 2CHCF2, CHF2CF2, CF2=C (CF3), CF3CF=CF, CF2=CFCF2, CF3CH=CF, CF3CHBrCF2, CF3CFBrCF2, or CF2BrCF2and Z2 is selected from the group comprisingCHF2,CF3,CH2CF3,CH2Br,CFBr2, orCF2Br.
116. The mixture of claim 110, wherein the extinguishing compound comprises about 0. 1 % (v/v) to about 10% (v/v) of the space.
117. The mixture of claim 110, wherein the extinguishing compound comprises CF3CHFCF20CHF2.
118. The mixture of claim 111, wherein the CF3CHFCF20CHF2 comprises from about 0.1 % (v/v) to about 6% (v/v) of the space.
119. 7 114. The mixture of claim 111, wherein the CF3CHFCF20CHF2 comprises about 6% (v/v) of the space.
120. The mixture of claim 110, wherein the extinguishing compound consists essentially of CF3CHFCF20CHF2.
121. The mixture of claim 110, wherein the extinguishing compound consists of CF3CHFCF20CHF2.
122. The mixture of claim 110, wherein the extinguishing compound comprises CF3CHFCF20CF3.
123. The mixture of claim 117, wherein the CF3CHFCF20CF3 comprises from about 4% (v/v) to about 6% (v/v) of the space.
124. The mixture of claim 117, wherein the CF3CHFCF20CF3 comprises about 5% (v/v) of the space.
125. The mixture of claim 110, wherein the extinguishing compound consists essentially of CF3CHFCF20CF3.
126. The mixture of claim 110, wherein the extinguishing compound consists of CF3CHFCF20CF3.
127. A method for one or more of extinguishing, suppressing or preventing a fire in a space by introducing to the space a mixture comprising an extinguishing compound having the general formula Z'OZ, wherein Z'is selected from the group comprising CF3CHFCF2, CF3CF2CF2, (CF3) 2CHCF2, CHF2CF2, CF2=C (CF3), CF3CF=CF, CF2=CFCF2, CF3CH=CF, CF3CHBrCF2, CF3CFBrCF2, or CF2BrCF2 and z2 is selected from the group comprisingCHF2, CF3,CH2CF3,CH2Br,CFBr2, or CF2Br.
128. The method of claim 122, wherein the extinguishing compound comprises about 0. 1% (v/v) to about 10% (v/v) of the space.
129. The method of claim 122, wherein the extinguishing compound comprises CF3CHFCF20CHF2.
130. The method of claim 124, wherein the CF3CHFCF20CHF2 comprises from about 0. 1% (v/v) to about 6% (v/v) of the space.
131. The method of claim 124, wherein the CF3CHFCF20CHF2 comprises about 6% (v/v) of the space.
132. The method of claim 122, wherein the extinguishing compound comprises CF3CHFCF20CF3.
133. The method of claim 127, wherein the CF3CHFCF20CF3 comprises from about 4% (v/v) to about 6% (v/v) of the space.
134. The method of claim 127, wherein the CF3CHFCF20CF3 comprises about 5 % (v/v) of the space.
135. A fire extinguishing, preventing or suppressing system configured to introduce to a space a mixture comprising an extinguishing compound having the general formula Z'OZ2, wherein Z'is selected from the group comprising CF3CHFCF2, CF3CF2CF2, (CF3) 2CHCF2, CHF2CF2, CF2=C (CF3), CF3CF=CF, CF2=CFCF2, CF3CH=CF, CF3CHBrCF2, CF3CFBrCF2, or CF2BrCF2and Z2 is selected from the group comprisingCHF2,CF3,CH2CF3,CH2Br,CFBr2, orCF2Br.
136. The system of claim 130, wherein the extinguishing compound comprises about 0. 1 % (v/v) to about 10% (v/v) of the space.
137. The system of claim 130, wherein the extinguishing compound comprises CF3CHFCF20CHF2.
138. The system of claim 132 wherein the CF3CHFCF20CHF2 comprises from about 0. 1 % (v/v) to about 6% (v/v) of the space.
139. The system of claim 132 wherein the CF3CHFCF20CHF2 comprises about 6% (v/v) of the space.
140. The system of claim 130 wherein the extinguishing compound comprises CF3CHFCF20CF3.
141. The system of claim 135, wherein the CF3CHFCF20CF3 comprises from about 4% (v/v) to about 6% (v/v) of the space.
142. The system of claim 135, wherein the CF3CHFCF20CF3 comprises about 5 % (v/v) of the space.
Description:
METHODS FOR PREPARING ETHERS, ETHER COMPOSITIONS, FLUOROETHER FIRE EXTINGUISHING SYSTEMS, MIXTURES AND METHODS TECHNICAL FIELD [0001] The present invention is directed to novel ether compounds and in particular aspects halogenated ether compounds and in other embodiments fluorinated ether compounds. Other aspects of the present invention are also directed to the production of these ether compounds and their uses.

[0002] Certain aspects of the present invention are directed to fluoroether fire extinguishing agents and methods for extinguishing fires using the fluoroethers.

BACKGROUND OF THE INVENTION [0003] Bromine, chlorine, and iodine containing halogenated chemical agents are in general thought to be effective fire extinguishing agents. One mechanism for flame suppression is the radical trap mechanism proposed by Fryburg in Review of Literature Pertinent to Fire Extinguishing Agents and to Basic Mechanisms Involved in Their Action, NACA-TN 2102 (1950). Some have found that the effectiveness of the halogens are on a molar basis in the order CI<Br<l, as reported by Malcom I Vaporizing Fire Extinguishing Agents, Report 117, Dept. of Army Engineering Research and Development Laboratories, Fort Bevoir, VA, 1950 (Project-8-76-04-003).

[0004] The use of iodine-containing compounds as fire extinguishing agents has been avoided in certain circumstances due to the expense of their manufacture or due to toxicity considerations. Until recently, fire extinguishing agents presently in common use were all bromine-containing compounds; Halon 1301 (CF3Br), Halon 1211 (CF2BrCI) and Halon 2402 (BrCF2CF2Br). The effectiveness of these volatile bromine-containing compounds in extinguishing fires has been described in U. S. Pat. No. 4,014, 799 to Owens. Certain chlorine containing compounds are also known to be effective extinguishing agents, for example Halon 251 (CF3CF2CI) as described by Larsen in U. S.

Pat. No. 3,844, 354.

[0005] Although the above-named bromine or chlorine-containing Halons are effective fire fighting agents, those agents containing bromine or chlorine are asserted by Docket No. PC3-045 some to be capable of the destruction of the earth's protective ozone layer. Also, some believe these agents may also contribute to a greenhouse warming effect, sometimes corresponding to a high global warming potential.

[0006] More recently, hydrofluorocarbons have been proposed forfire suppression, for example in U. S. Pat. No. 5,124, 053. However, these compounds may demonstrate a relatively high global warming potential.

SUMMARY OF THE INVENTION [0007] One embodiment of the present invention provides processes for producing halogenated ethers from olefins and alcohols. In one aspect, the present invention provides processes for producing halogenated ethers from olefins and methanol. In a particular aspect, the present invention provides a continuous process of producing halogenated ethers by combining olefins and alcohols in the presence of an aqueous solution containing a base.

[0008] Another aspect of the present invention provides processes for the production of halogenated ether intermediates useful in the production of fluoroethers. In one aspect, the halogenated ether intermediate can be produced by combining the ether with a halogenating agent in the presence of ultraviolet (uv) radiation.

[0009] In a further aspect of the present invention, halogenated ether intermediates can be converted to fluoroethers. In one aspect, CF3CHFCF2OCCI3 can be fluorinated in the presence of gaseous HF and a catalyst to produce CF3CHFCF20CF3. In one aspect, CF3CHFCF20CHF2 can be produced by reacting CF3CHFCF20CHCI2 with HF in the presence of a catalyst.

[0010] In another aspect, the halogenated ether intermediate can be fluorinated in the presence of liquid hydrogen fluoride (HF) to obtain the fluoroether intermediate which can subsequently be fluorinated to form a fluoroether. In an exemplary aspect, CF3CHFCF20CCI3 can be fluorinated in the presence of liquid HF to form CF3CHFCF20CCI2F which can subsequently be fluorinated in the presence of gaseous HF to form CF3CHFCF20CF3.

[0011] The fluoroethers of this invention may be produced via multi-step routes. For example, CF3CHFCF20CF2H may be prepared via a three step process that includes: i. reaction of methanol with commercially available hexafluoropropene (CF3CF=CF2) in the presence of base to produce CF3CHFCF20CH3 ; ii. chlorination of CF3CHFCF20CH3 with Cis to produce CF3CHFCF20CHCI2 ; and iii. fluorination of CF3CHFCF20CHCI2 with HF to produce the final product CF3CHFCF20CF2H.

[0012] In still another embodiment of the present invention, fluoroethers of the present invention are used as extinguishants (including streaming and total flooding agents).

[0013] The foregoing and other objects, advantages and features of the present invention may be achieved by employing saturated or unsaturated, fluoroethers and blends thereof with other agents as fire extinguishants for use in fire extinguishing methods and apparatus. Methods of according to the present can involve introducing to a fire a saturated or unsaturated, fluoroether in a fire extinguishing concentration and maintaining such concentration until the fire is extinguished. Specific saturated fluoroethers of this invention include: CF3CHFCF20CH3, CF3CHFCF20CH2F, CF3CHFCF20CF2H, CF3CHFCF20CF3, (CF3) 2CHCF20CH3, (CF3) 2CHCF20CH2F, (CF3) 2CHCF20CHF2, and (CF3) 2CHCF20CF3.

[0014] These fluoroethers may be used alone, in admixture with each other or as blends with other fire extinguishing agents. Suitable extinguishing agents ("blends") for admixture with the hydrofluoroethers include CF3CHFCF3, CF3CF2CF2H, CF3CH2CF3, CF3CF2H, and CF3H.

[0015] In still another embodiment of the present invention, fluoroethers of the present invention can be used as solvents, refrigerants, blowing agents, etchants, anesthetics, and propellants. Novel compositions of matter such as CF3CHFCF20CF3 are also provided.

[0016] The above and other embodiments, aspects, alternatives, and advantages of the present invention will become more apparent from the following detailed description of the present invention taken in conjunction with the drawings.

BRIEF DESCRIPTION OF THE DRAWINGS [0017] Fig. 1. is a diagram of one embodiment of ether production in accordance with an aspect of the present invention.

[0018] Fig. 2 is an illustration of an application of extinguishing mixtures in accordance with an aspect of the present invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS [0019] According to an embodiment of the present invention fluoroethers are produced and can be utilized to extinguish combustion. For purposes of this disclosure the term fluoroethers includes all compounds having an ether group and a fluorine atom. Examples of these compounds include, but are not limited to perfluoroethers, hydrofluoroethers, fluorohalogenated ethers, and/or hydrofluorohalogenated ethers.

Exemplary aspects of the present invention are described with reference to Figures 1 and 2.

[0020] Referring now to Fig. 1, a reaction apparatus 10 including a source of olefin 1, a source of alcohol 2, and basic aqueous solution 4 (with the olefin, alcohol, and basic aqueous solution being reagents 7) is shown. The apparatus further includes a reaction vessel 3. In one aspect, olefin 1, alcohol 2, and a basic aqueous solution 4 are combined to form an ether containing reaction product 5. Reagents can be combined in a batch, semi-continuous, or continuous fashion. Reaction product 5 can remain in reaction vessel 3 and/or be transferred to a separation vessel 6, as shown, where a crude ether product 8 is separated from reagents 7. Reagents 7 can then be returned to reaction vessel 3 to react in the presence of additional or remaining basic aqueous solution 4.

[0021] Depending on the specific olefins and alcohols selected as reagents, the ether containing reaction product may be removed from reaction vessel 3 in a number of forms including as a gas or as a top, middle or bottom liquid layer. Likewise, the separation of crude ether 8 from reagents 7 may involve removal of crude ether product 8 as a gas or as a top, middle, or bottom liquid layer and otherwise removal of reagents 7 as a gas or a top, middle, or bottom layer. Consequently, the return of reagents 7 to reaction vessel 3 may take the form of the return of a gas and/or liquid composition.

[0022] Olefin 1 can have the general formula R' (R2) C=CXY. Olefin 1 can generally be referred to as a hydrogenated, halogenated, and/or a perhalogented olefin. R'can include lone halogens, lone hydrogens, halogenated alkyl groups, hydrogenated alkyl groups or perhalogenated alkyl groups either alone or in combination. For purposes of this disclosure, the halogenated alkyl groups includes all alkyl groups having at least one halogen, regardless of what the remaining elements of the alkyl might be. For example, and by way of example only, halogenated alkyl groups include but are not limited to-CHFCI,-CF3, or-CF2CI. R2 can include lone halogens, lone hydrogens, halogenated alkyl groups, hydrogenated alkyl groups or perhalogenated alkyl groups either alone or in combination. R'and R2 can be the same or different groups. In one aspect R'includes CF3-or F. In one aspect of the present invention, R2 can be H or F. In one combination, R'can be F and R2 can be F.

In another combination, R'can be F and R2 can be H.

[0023] For purposes of this disclosure, X and Y can generally represent hydrogen and/or the halogens 1, Br, Cl, and/or F. In one aspect of the present invention, X and Y can be the same element, for example, X can be F and Y can be F.

In an exemplary aspect, X and Y can be different elements, for example, X can be F and Y can be H.

[0024] According to an aspect of the present invention, olefin 1 includes CF3CF=CF2 (hexafluoropropene, HFP), CF3CH=CF2 (pentafluoropropene, PFP), or CF2=CF2 (tetrafluoroethene, TFE). In certain aspects of the present invention, olefin 1, can comprise, consist, and/or consist essentially of CF3CF=CF2. In exemplary aspects, olefin 1 can comprise, consist, and/or consist essentially of CF2=CF2.

[0025] Alcohol 2 includes hydrogenated and halogenated alcohols. According to an aspect of the present invention, alcohol 2 can include methanol (CH30H), ethanol (CH3CH20H), and/or isopropanol ((CH3) 2CHOH).

[0026] Basic aqueous solution 4 can include sufficient base to ensure the formation of an alkoxide upon combination with an alcohol. Bases that can be used to form the alkoxide include those of sodium and potassium such as sodium hydroxide (NaOH) or potassium hydroxide (KOH). In an aspect of the present invention, basic aqueous solution includes KOH.

[0027] According to an aspect of the present invention, basic aqueous solution 4 includes an aqueous solution having a KOH concentration of 10-45% (wt. /wt.). This KOH solution can be combined with alcohol 2 in reaction vessel 3 to form a first reactant mixture having an alcohol concentration of 50-60% (wt. /wt.) and a KOH concentration of 5-20% (wt./wt.). Olefin 1 can then be combined with the first reactant mixture in reaction vessel 3. Reaction vessel 3 can have a temperature from about- 10°C to about 50°C.

[0028] According to one aspect, the bottom organic phase containing crude ether 8 can be separated from the top mixture that can include reagents 7. In an exemplary aspect reagents 7 can be returned to reaction vessel 3.

[0029] The crude ether 8 of the present invention can generally be referred to as an ether or halogenated ether and have the general formula R3CXY-0-R4. The R3 group can include hydrogenated alkyl groups, halogenated alkyl groups, and/or perhalogenated alkyl groups. For example, and by way of example only, R3 can include CF3CHF-, CF3CH2-, and/or CHF2-. The R4 group can include hydrogenated alkyl groups, halogenated alkyl groups, and/or perhalogenated alkyl groups. For example, and by way of example only, R4 can include-CH3,-CH2CH3, and/or- CH (CH3) 2. In an aspect of the present invention, the halogenated ether includes CF3CHFCF20CH3. In another aspect of the present invention, the halogenated ether includes CF3CH2CF20CH3. In still another aspect of the present invention, the halogenated ether includes CHF2CF20CH3. Non-limiting examples 1-3 demonstrate aspects of ether preparation according to the present invention.

[0030] According to another aspect of the present invention a halogenated ether intermediate can be formed by reacting an ether with a halogen in the presence of actinic energy. This reaction can be carried out in a photochemical reactor. The reactor may be configured to provide actinic energy to its content from an internal and/or an external source. For example, and by way of example only, a medium pressure mercury lamp (100 watt, 11.49 watt total radiant energy) can be utilized to provide the necessary radiation from within the reactor. Other configurations may include the use of 90% 3500 angstrom range of photon black light providing 24 watts of total radiant energy. The reactor may be cooled, for example, from a municipal water source.

[0031] The halogen can include chlorine (C12). Depending on the product desired, halogens such as bromine or iodine may be utilized as well. The reaction can be performed at a temperature from about 10°C to about 70°C.

[0032] In an exemplary aspect, methods include providing a photochemical reactor containing an ether. The ether can have the general formula R3CXY-0-R4, as described above.

[0033] The halogenated either intermediate can have the general formula R5CXY-0-R6. The R5 group can include hydrogenated alkyl groups, halogenated alkyl groups, and/or perhalogenated alkyl groups. For example, and by way of example only, R5 can include CF3CHF-, CF3CCIF-, CF3CH2-, CF3CHCI-, CF3CC12-, CHF2-, and/or CCIF2-. The R6 group can include halogenated alkyl groups or perhalogenated alkyl groups. For example, and by way of example only, R6 can include-CH2CI,-CHC12, and/or-CCI3. In an aspect of the present invention, the halogenated ether intermediate can include CF3CHFCF20CCI3. In another aspect of the present invention, the halogenated ether intermediate can include CF3CHFCF20CHCI2. In still another aspect of the present invention, the halogenated ether intermediate can include CF3CHFCF20CH2CI. In an exemplary aspect, the halogenated ether intermediate can include CF3CCIFCF20CCI3.

[0034] In certain aspects of the present invention, two halogenated ether intermediates useful in the production of fluoroethers can be produced according to the present invention. In one aspect, the ether CF3CHFCF20CH3 can be chlorinated according to the present invention to produce a mixture of halogenated ether intermediates such as CF3CHFCF20CHCI2 and CF3CHFCF20CC13. Non-limiting Example 4 demonstrates an aspect of the halogenated ether intermediate production methods according to the present invention.

[0035] Another aspect of the present invention provides methods for converting halogenated ether intermediates to useful fluoroethers. Aspects of the present invention provide efficient processes for fluorinating halogenated ethers to produce heretofore unknown compounds.

[0036] In an aspect of the present invention, the halogenated ether intermediate can have the general formula R5CXY-O-R6, as described above. In an aspect of the present invention, the halogenated ether intermediate can be selectively fluorinated in the presence of HF and a catalyst to produce a fluoroether.

[0037] The catalyst can include a chromium/carbon catalyst that has been pre- fluorinated. The catalyst utilized may take pure or supported forms. Supports include but are not limited to those of activated carbon. The catalysts themselves include but are not limited to such catalysts as those of chromium, nickel, iron, vanadium, manganese, cobalt, and/or zinc. The preparation can occur from about 100 °C to about 300 °C. In certain aspects, the temperature of the reaction is about 200 °C.

[0038] The fluoroether produced can have the general formula R'-O-R8. The R7 group can include hydrogenated alkyl groups, hydrofluorohalogenated alkyl groups, hydrofluorinated alkyl groups, fluorohalogenated alkyl groups, and/or perfluorinated alkyl groups. For example, and by way of example only, R7 can include CF3CHFCF2-, CF3CCIFCF2-, CF3CF2CF2-, CF3CH2CF2-, CF3CHCICF2-, CF3CC12CF2-, CHF2CF2-, CF3CF2-, and/or CCIF2CF2-. The R group can include hydrofluorohalogenated alkyl groups, hydrofluorinated alkyl groups, fluorohalogenated alkyl groups, and/or perfluorinated alkyl groups. For example, and by way of example only, R8 can include- CFCI2,-CF2CI,-CF3,-CHFCI,-CF2H, and/or CFH2. In an aspect of the present invention, the fluoroether includes the hydrofluoroether CF3CHFCF20CF3. In another aspect of the present invention, the fluoroether includes the hydrofluoroether CF3CHFCF20CHF2. In still another aspect of the present invention, the fluoroether includes the perfluorinated ether CF3CF2CF20CF3.

[0039] According to one aspect of the present invention, an ether can be fluorinated in the presence of liquid hydrogen fluoride (HF). In one aspect, an ether having at least one of the halogens 1, Br, or Cl can be fluorinated in the presence of liquid HF to produce a fluoroether. The fluoroether produced according to this aspect of the present invention can be characterized as having at least one more fluorine atom than the ether. For example, and by way of example only, the ether CF3CHFCF20CC13 can be fluorinated in the presence of liquid HF to produce the fluoroether CF3CHFCF20CFCI2. In one aspect of the present invention, this fluorination can occur from about 40°C to about 120°C. In one aspect of the present invention, this fluorination can occur at approximately 70°C.

[0040] The fluoroether produced according to an aspect of the present invention may be utilized as starting materials for other aspects of the present invention.

Accordingly, the ether can be fluorinated at about 70°C and subsequently fluorinated at about 200°C. The ether may also be fluorinated at about 70°C and subsequently fluorinated at about 230°C or 280°C. For example, and by way of example only, the ether CFsCHFCFzOCCts can be fluorinated in the presence of liquid HF to produce the fluoroether CF3CHFCF20CFCI2, which can be fluorinated in the presence of HF and a catalyst as described above to produce the hydrofluoroether CF3CHFCF20CF3.

[0041] An embodiment of the present invention also provides multi-step synthetic processes for the production of fluoroethers. According to one aspect of the present invention, methods are provided for manufacturing fluoroethers that include combining an alcohol with an olefin to produce an ether. Subsequently, reacting the ether with a halogenating agent to produce a halogenated ether intermediate and then fluorinating the halogenated ether intermediate with HF to from a fluoroether. In another aspect, the halogenated ether intermediate can be fluorinated with HF at a first temperature to from a fluoroether intermediate. The fluoroether intermediate can then be fluorinated with HF at a second temperature to form a fluoroether.

[0042] An embodiment of the present invention also provides halogenated ether compounds. Generally, these ether compounds have the formula R90R10. Generally, R9 can be partially or fully halogenated, saturated or unsaturated, organic groups, and R10 can be partially or fully halogenated, saturated or unsaturated organic groups. In particular aspects, these halogenated ether compounds include CF3CHFCF20CF3.

The structure of CF3CHFCF20CF3 was confirmed by gas chromatography mass spectrometry (GC-MS) and. fluorine (19F), proton ('H), and carbon (13C) nuclear magnetic resonance (NMR). The boiling point of this compound was also determined.

GC-MS (m/e) : 69 (CF3), 82 (CF3CH), 101 (CF3CHF), 129 (CHFCF20CF or CHCF20CF2), 135 (CF20CF3), 151 (CF3CHFCF2), 217 (CF3CHFCF20CF2) High Resolution MS Theoretical : 235.98837 Found: 235.98726 NMR: F'9 (282 MHz, CFCI3) : 6-55. 4 (t, 3F, J = 8.9 Hz), -75.3 (m, 3F), - 81. 4 (m, 2F), -211. 5 (d, t, q, 1 F, J = 43.64, 10.91 Hz) ppm H1 : (300 MHz, CDCI3) : 5 4.86 (d, t, q, 1 H, J = 43.8, 5.51, 5.98 Hz) ppm C13 : (75 MHz, CDC13) : 5 77 (t, J = 31.78 Hz), 84.1 (d, t, q, J = 204.69, 35.79, 35.79 Hz), 119.2 (q, J = 267.68 Hz), 112-125 (m) ppm Boiling point : 23-24°C.

[0043] Non-limiting Examples 5,6, 7, and 8 demonstrate preparations according to aspects of the present invention.

[0044] The present invention also provides fire extinguishing mixtures which comprise fluoroether extinguishing agents that can extinguish fires through inertion, and/or dilution, as well as, chemical, physical, and/or thermal extinguishment methods.

Thermal extinguishment includes"cooling"a combustion. The present invention also provides methods of extinguishing, preventing, and/or suppressing a fire using such fire extinguishing mixtures. The present invention further provides fire extinguishing, preventing, and/or suppressing systems for delivering such fire extinguishing mixtures.

Exemplary aspects of the present invention are described with reference to Fig. 2.

[0045] Referring to Fig. 2, a space 27 configured with a fire extinguishing system 11 is shown. Fire extinguishing system 11 includes an extinguishing agent storage vessel 13 contiguous with an extinguishing agent dispersing nozzle 17. As depicted, a combustion 21 occurs within a pan 23 on a pedestal 25. An extinguishing mixture 19 exists within space 27 and is applied to combustion 21 to substantially extinguish the flame.

[0046] While depicted in two dimensions, space 27, for purposes of this disclosure, should be considered to have a volume determined from its dimensions (e. g. , width, height and length). While Fig. 2 illustrates a system configured for extinguishing fires within a space that, as illustrated, appears to be enclosed, the application of the mixtures, systems, and methods of the present invention are not so limited. In some aspects, the present invention may be used to extinguish fires in open spaces, as well as, confined spaces.

[0047] Alternatively, the fluoroether extinguishing agents may be applied to a fire through the use of conventional portable fire extinguishing equipment. Fluoroether containing systems in accordance with this invention may be conveniently pressurized with diluents up at any desirable pressure up to about 600 psig at ambient conditions.

[0048] All combustion suitable for extinguishment, suppression or prevention using the mixtures of the present invention or utilizing the methods and systems according to the present invention, are at least partially surrounded by a space. The available volume of this space can be filled with the compositions of the present invention to extinguish, suppress, and/or prevent combustion. Typically, the available volume is that volume which can be occupied by a liquid or a gas [i. e. that volume within which fluids (gases and liquids) can exchange]. Solid constructions typically are not part of the available volume.

Docket No. PC3-045 [0049] Furthermore, Fig. 2 illustrates a single extinguishing agent storage vessel 13. It should be understood that extinguishing mixture 19 can be provided to room 27 from multiple extinguishing agent storage vessels 13 and the present invention should not be limited to mixtures, methods, and/or systems that can be provided from a single vessel nor methods or systems that utilize a single vessel. Generally, combustion 21 is extinguished when extinguishing mixture 19 is introduced from vessel 13 through nozzle 17 to space 27. It should also be understood, that while Fig. 2 illustrates a single nozzle 17, multiple nozzles may be utilized, and the present invention should not be limited to mixtures, methods, and/or systems utilizing a single nozzle.

[0050] In one aspect of the present invention, extinguishing mixture 19 can comprise, consist essentially of, and/or consist of a fluoroether extinguishing agent. In another aspect, extinguishing mixture 19 can comprise, consist essentially of, and/or consist of a fluoroether extinguishing agent and a suppressing additive and/or other fire extinguishing agents.

[0051] The suppressing additive employed can include diluent gases, water, and/or mixtures thereof. Exemplary diluent gases can include nitrogen, argon, helium, carbon dioxide, and/or mixtures thereof. In an exemplary aspect, these gases can deprive fires of necessary ingredients, such as oxygen and/or fuel. In the same or other aspects, these diluent gases resist decomposition when exposed to combustion.

In some cases, these gases are referred to as inert gases. An exemplary diluent gas can comprise, consist essentially of, and/or consist of nitrogen.

Docket No. PC3-045 [0052] Generally, the fluoroether extinguishing agent can have the formula R9OR10. Generally, R9 can be partially or fully halogenated, saturated or unsaturated, organic groups, and R10 can be partially or fully halogenated, saturated or unsaturated organic groups. More specifically, the fluoroether extinguishing agents of the present invention can have the general formula Z1 o z2. The Z'group can include CF3CHFCF2-, CF3CF2CF2-, (CF3) 2CHCF2-, CHF2CF2-, CF2=C (CF3)-, CF3CF=CF-, CF2=CFCF2-, CF3CH=CF-, CF3CHBrCF2-, CF3CFBrCF2-or CF2BrCF2-. The Z2 group can include-CHF2,-CF3,-CH2F,-CH2Br,-CFBr2,-CHFBr or-CF2Br. In particular aspects the fluoroether extinguishing agent includes CF3CHFCF20CF3 and/or CF3CHFCF20CHF2, and/or CHF2CF20CF3.. GenerallyFluoroether extinguishing agent concentrations lying in the range from about 3 to about 15% in air, preferably from about 5 to about 10% in air, on a v/v basis can be employed.

[0053] These fluoroether extinguishing agents may be used alone, as admixtures with each other or as blends with other fire extinguishing agents. As admixtures with fire extinguishing agents, concentrations lying in the range from about 3 to about 15%, and/or from about 5 to about 10% in air, on a v/v basis, can be employed. Where the fluoroether extinguishing agents of the present invention are employed in admixture with other fire extinguishing agents ("blends"), the fluoroether extinguishing agents can comprise of at least about 10% by weight of the blends, and the overall concentration of the blend lies in the range from about 3 to about 15% and/or from about 5 to about 10% in air, on a v/v basis. The fire extinguishing agents of this invention are suitable for use in both total flooding and portable fire suppression applications.

[0054] It should be understood that the % (v/v) values set forth in this description and in the claims are based on space volume and refer to the design concentration as adopted and described by the National Fire Protection Association in NFPA 2001, Standard on Clean Agent Fire Extinguishing, 2000 edition.

[0055] The equation used to calculate the concentrations of extinguishing compounds has likewise been adopted by the National Fire Protection Association and is as follows : W = V/s (C/100-C) Where : W = weight of extinguishing compound (kg) V = volume of test space (m3) s = specific volume of extinguishing compound at test temperature (m3/kg) C = concentration (% (v/v)) [0056] Suitable fire extinguishing agents for blends with the fluoroether extinguishing agents include : difluoromethane (HFC-32), chlorodifluoromethane (HCFC-22), 2, 2-dichloro-1, 1, 1-trifluoroethane (HCFC-123), 1, 2-dichloro-1, 1,2- trifluoroethane (HCFC-123a), 2-chloro-1, 1,1, 2-tetrafluoroethane (HCFC-124), 1-chloro- 1,1, 2, 2-tetrafluoroethane (HCFC-124a), pentafluoroethane (HFC-125), 1,1, 2,2- tetrafluoroethane (HFC-134), 1,1, 1, 2-tetrafluoroethane (HFC-134a), 3, 3-dichloro- 1,1, 1,2, 2-pentafluoropropane (HCFC-225ca), 1, 3-dichloro-1, 1,2, 2,3- pentafluoropropane (HCFC-225cb), 2, 2-dichloro-1, 1,1, 3, 3-pentafluoropropane (HCFC- 225aa), 2, 3-dichloro-1, 1,1, 3, 3-pentafluoropropane (HCFC-225da), 1,1, 1,2, 2,3, 3- heptafluoropropane (HFC-227ca), 1,1, 1,2, 3,3, 3-heptafluoropropane (HFC-227ea), 1,1, 1,2, 3, 3-hexafluoropropane (HFC-236ea), 1,1, 1,3, 3, 3-hexafluoropropane (HFC- 236fa), 1,1, 1,2, 2, 3-hexafluoropropane (HFC-236cb), 1,1, 2,2, 3, 3-hexafluoropropane (HFC-236ca), 3-chloro-1, 1, 2,2, 3-pentafluoropropane (HCFC-235ca), 3-chloro-1, 1, 1, 2,-2- pentafluoropropane (HCFC-235cb), 1-chloro-1, 1,2, 2, 3-pentafluoropropane (HCFC- 235cc), 3-chloro-1, 1,1, 3, 3-pentafluoropropane (HCFC-235fa), 1,1, 1,3, 3- pentafluoropropane (HFC-245fa), 3-chloro-1, 1,1, 2,2, 3-hexafluoropropane (HCFC- 226ca), 1-chloro-1, 1,2, 2,3, 3-hexafluoropropane (HCFC-226cb), 2-chloro-1, 1,1, 3,3, 3- hexafluoropropane (HCFC-226da), 3-chloro-1, 1,1, 2,3, 3-hexafluoropropane (HCFC- 226ea), and 2-chloro-1, 1,1, 2,3, 3-hexafluoropropane (HCFC-226ba), and inert gases such as nitrogen.

[0057] The fluoroether fire extinguishing agents of the present invention may be effectively employed at substantially any minimum concentrations at which fire may be extinguished, the exact minimum level being dependent on the particular combustible material, the particular fluoroether extinguishing agent, and the combustion conditions.

In general, however, acceptable results are achieved where the fluoroether extinguishing agents or mixtures and blends thereof are employed at a level of at least about 3% (v/v). Where fluoroether extinguishing agents alone are employed, acceptable results are achieved with fluoroether extinguishing agent levels of at least about 5% (v/v). Likewise, the maximum amount to be employed may be governed by matters of economics and potential toxicity to living things. About 15% (v/v) provides a convenient maximum concentration for use of fluoroether extinguishing agents and mixtures and blends thereof in occupied areas. Concentrations above 15% (v/v) may be employed in unoccupied areas, with the exact level being determined by the particular combustible material, the fluoroether extinguishing agents (or mixture or blend thereof) chosen, and the conditions of combustion. A concentration of the fluoroether extinguishing agents, mixtures, and blends in accordance with an aspect of this invention lies in the range of about 5 to 10% (v/v).

[0058] In particular aspects, an extinguishing mixture comprising, consisting essentially of, and/or consisting of CF3CHFCF20CF3 may be employed.

CF3CHFCF20CF3 can be employed at concentrations of about 5 % (v/v).

[0059] Some of the applications of the fluoroether extinguishing agents of the present invention are the extinguishing of liquid and gaseous fueled fires, the protection of electrical equipment, ordinary combustibles such as wood, paper, and textiles, hazardous solids, and the protection of computer facilities, data processing equipment, and control rooms.

[0060] The novel ethers according to the present invention can also be introduced to a fire for suppression purposes as a liquid or gas or combination of both.

This is sometimes referred to as utilizing the composition as a streaming agent. The novel ethers according to the present invention can be introduced to fires in combination with other compounds as blends.

[0061] In still another embodiment of the present invention, ethers of the present invention are used either alone or as blends as extinguishants, including streaming and total flooding agents, solvents, refrigerants, blowing or expansion agents, etchants, anesthetics, propellants, and as power cycle working fluids.

[0062] The novel ethers of the present invention may be used to produce refrigeration by condensing the ether either alone or as a blend and thereafter evaporating the condensate in the vicinity of a body to be cooled. The novel ethers of the present invention may also be used to produce heat by condensing the refrigerant in the vicinity of the body to be heated and thereafter evaporating the refrigerant.

[0063] The invention will be further described with reference to the following specific examples. However, it will be understood that these examples are illustrative in nature and not restrictive in nature. Where referenced, G. C. area % corresponds to percentage area of peak in comparison to all peaks generated when the respective sample is analyzed by a gas chromatograph equipped with a flame ionization detector and a silica-plot column.

Example 1: Ether Preparation aq. KOH CF3CF=CF2+CH30H o CF3CHFCF20CH3 [0064] An aqueous 45% (wt. /wt.) KOH solution is added to methanol to produce a mixture containing 60% (wt./wt.) methanol and 18% (wt. /wt.) KOH. This mixture is placed in a three-neck glass flask equipped with a dry ice condenser, a dip tube, and a thermometer. HFP is fed through the dip tube into the solution at-3°C to 0°C. The condenser is kept at-30 to-40°C in order to condense unreacted HFP back into the reactor. A water bath is used to control the exothermic reaction. When the solution becomes a milky suspension, the mixture is drawn out of the reactor and allowed to phase separate. The bottom organic phase containing crude CF3CHFCF20CH3 is separated out, and the top mixture with additional methanol is fed back to the reactor.

Four aliquots of the crude CF3CHFCF20CH3 are collected at time intervals and analyzed by gas chromatography for lights, unreacted olefin, ether, and heavies. The results are shown below in Table 1.

Table 1 (G. C. Area %) Aliquot Crude Lights Olefin CF3CHFCF20CH3 Heavies Product CF3CF=CF2 Collected (g) A 22. 5 trace 4. 04 89. 09 6. 12 B 18.5 0.46 3.49 88.72 6.73 C 26. 6 0. 44 3. 49 85. 59 9. 73 D 97. 84 trace 5. 14 87. 78 6. 11 Overall Crude Yield 84.9% based on HFP Example 2: Ether Preparation aq. KOH [0065] Example 2 is performed as Example 1 with the modification that the reaction is performed using an aqueous mixture having 13% (wt. /wt.) KOH and 57% (wt. /wt.) methanol at 15°C to 25°C, and two collection aliquots are taken and analyzed by gas chromatography. The gas chromatography results are reported below in Table 2.

Table 2 G. C. Area % Aliquot Crude Lights Olefin CF3CHFCF20CH3 Heavies Product CF3CF=CF2 Collected (g) A 77. 2 trace 0. 65 94. 99 3. 68 B 45 trace 1. 69 95. 08 2. 12 Example 3: Ether Preparation aq. KOH [0066] Example 3 is performed as example 1 with the modification that the reaction is performed in a 600 cc stainless steel pressure reactor using an aqueous mixture having 10% (wt./wt.) KOH and 50% (wt./wt.) methanol. The reactor is cooled to - 10°C and then pressurized with tetrafluoroethylene (CF2=CF2) which is first passed through a bubbler filled with a-pinene. The reaction is carried out at 60°C under 60 psig to generate 97% (G. C. Area %) pure CHF2CF20CH3. No polytetrafluoroethylene is visually observed.

Example 4: Preparation of Halogenated Ether Intermediates uv light [0067] This reaction is carried out in a jacketed glass photochemical reactor cooled with tap water. A medium pressure mercury lamp (100 watt, 11. 49 watt total radiant energy) is used for the reaction. Chlorine gas is bubbled into 400g of liquid CF3CHFCF20CH3 at 20°C-30°C and by-product HCI is vented to a water scrubber.

The reaction is stopped, the crude reaction mixture is sampled, analyzed by gas chromatography, and then distilled. Two major products are generated in the reaction, CF3CHFCF20CHC12 [37% (G. C. Area %), b. p. 75°C@42 cmHg] and CF3CHFCF20CCI3 [61% (G. C. Area %), b. p. 82°C@32 cmHg] for a total of 482g of recovered crude material.

Example 5: Preparation of Fluoroethers Cr/AC-gas phase [0068] 50 g chromium/carbon catalyst is charged to a 0.5 inch x 24 inch long InconelS) tubing reactor which is heated using radiant heat. After pre-fluorinating the catalyst, HF and 99.8% pure CF3CHFCF20CHCI2 are fed into a reactor at predetermined rates and temperature under atmospheric pressure. The crude product is collected in an ice water scrubber and washed with H20, dried over MgS04, and purified by distillation. The boiling point of the resulting CF3CHFCF20CHF2 is 47-48°C and the density d=1.529. GC analysis of the collections corresponding to the parameters utilized are shown in the Table 3 below.

Table 3 Cr/AC-gas phase G. C. Area % Run Temp. (°C) HF/RfOCHC12 Contact RfOCHF2 RfOCHFCl RfOCHCl2 (mole ratio) time (sec) 1 120 7. 6/1 17 95. 6 1. 11 0. 23 2 125 6. 2/1 21 99. 2 0. 05 0. 003 3 150 7. 8/1 12 98. 3 0. 23 0. 003 4 150 6. 0/1 11. 6 98. 8 0. 05 0. 927 Rf=CF3CHFCF2 Example 6: Preparation of Fluoroethers Cr203-gas phase [0069] 38 g chromium (III) oxide catalyst is charged to a 0.5 inch x 14.125 inch long Inconel tubing reactor which is heated by a ceramic fiber heater. The catalyst is dried under nitrogen at 250-300°C. After drying, the catalyst is prefluorinated at 250- 300°C using a HF: N2 mixture (using a 1: 20 dilution). This prefluorination is continued until HF is detected exiting the reactor. At this point, the nitrogen is turned off, and the temperature is increased to 350°C. The catalyst is held under these conditions for 16 hours. After pre-fluorinating the catalyst, HF and CF3CHFCF20CC13 were fed into the reactor at predetermined rates and temperature under atmospheric pressure. The crude product is washed with H20, passed over calcium sulfate, and collected in a dry ice/acetone cooled trap. GC analysis of the reactor products corresponding to the parameters utilized are shown in the Table 4 below. The boiling point of the resulting CF3CHFCF20CF3 was 23-24°C.

Table 4 Cr203-gas phase G. C. Area % Run Temp. (°C) HF/RfOCCI3 Contact RfOCF3 CF3CHFCF3 (mole ratio) time (sec) 1 150 6. 04 8. 66 4. 28 15. 78 2 175 7. 12 8. 13 62. 00 12. 21 3 200 7. 12 8. 09 71. 89 13. 67 4 200 10. 87 19. 27 72. 58 15. 41 5 200 21. 07 8. 43 77. 06 12. 01 6 250 8.0 6.58 30.4 52. 23 Rf=CF3CHFCF2, tSynetix2) CP200A catalyst, PO Box 1, Billingham, TS23 1 LB, UK Example 7: Preparation of Fluoroethers Liquid phase [0070] 405 g of CF3CHFCF2OCCI3 produced according to the present invention is placed in a stainless steel pressure reactor. The reactor is cooled to-9°C and 76g of HF is added to the reactor. The reaction is carried out at 70°C, and a pressure of 300 psig is maintained in the reactor by venting the formed HCI to a water scrubber. 367.6 g crude product is collected. Gas chromatography analysis showed 91. 1% (G. C. Area %) of CF3CHFCF20CFCI2, 3.6% (G. C. Area %) of CF3CHFCF20CF2CI, and 3.5% (G. C.

Area %) of unreacted CF3CHFCF20CCI3.

Example 8: Preparation of Fluoroethers Cr/AC-gas phase [0071] Similar set-up and procedure was used as in Example 6 above. After pre-fluorinating the catalyst, HF and 99% pure CF3CHFCF20CFCI2 are fed into a reactor at predetermined rates and temperature under atmospheric pressure. The resulting crude product is passed through a heated scrubber and collected in a trap cooled by dry ice/acetone. This liquid is then dried over CaS04 and GC analysis of the collected crude mixtures is shown in Table 5. The collected material is combined and distilled to give two fractions of CF3CHFCF20CF3 of 99.6% and 99.77% G. C. assay at a boiling point of 23-24°C.

Table 5 Cr/AC-gas phase G. C. Area % Run Temp. (°C) HF/RfOCFC12 Contact HFC-227ea RfOCF3 RfOCF2CI (mole ratio) Time (sec) 1 230 9.4/1 9 3.7 91.7 2. 7 2 200 10/1 11 6. 6 66. 8 24. 4 Rf=CF3CHFCF2 EXAMPLE 9 [0072] This example demonstrates the desirable"throw"obtainable with the fire suppression agents of the present invention when employed in portable ("streaming") applications. The throw is the distance the stream of agent can be discharged; the longer the throw the better, as this allows extinguishment without approaching the fire at too close a distance, which can lead to exposure of the operator to fire and toxic fumes from the combustion process.

[0073] A 150 mL SS cylinder is equipped with an inlet tube and a dip tube connected via an on/off valve to a delivery nozzle. The cylinder is charged with 50 grams of CF3CHFCF20CF2H and then pressurized with nitrogen to the desired pressure. The cylinder contents are completely discharged and the throw distance noted (Table 6).

Table 6 Throw vs. Pressure for CF3CHFCF20CF2H System Pressure, psig Throw, feet 25 10 80 15 120 17 150 18 EXAMPLE 10 [0074] This example demonstrates the extinguishment of Class B fires with the agents of the present invention. A 150 mL SS cylinder is equipped with an inlet tube and a dip tube connected via an on/off valve to a delivery nozzle. The cylinder is charged with 30 grams of CF3CHFCF20CF2H and then pressurized with nitrogen to 120 psig. A 2 inch x 4 inch x 0.5 inch SS pan is filled with 20 mL of methanol. The methanol is ignited and allowed to burn for 30 seconds; the agent is then discharged from a distance of 4 feet onto the fire. The methanol fire can be extinguished in 1.5 seconds; a total of 16 grams of agent was discharged.

EXAMPLE 11 [0075] The method of Example 10 is employed with acetone, isopropanol, and heptane fuels. All fires are rapidly extinguished (see Table 7).

TABLE 7 Extinguishment with CF3CHFCF20CF2H Fuel Extinguishing Agent discharged, Time, seconds Grams Acetone 2.0 25 Isopropanol 1.5 21 Heptane 1.8 11 EXAMPLE 12 [0076] This example demonstrates the extinguishment of deep-seated Class A fires with the agents of the present invention. A 150 mL SS cylinder is equipped with an inlet tube and a dip tube connected via an on/off valve to a delivery nozzle. The cylinder is charged with 30 grams of CF3CHFCF20CF2H and then pressurized with nitrogen to 120 psig. A wood crib can be constructed of six layers of 6 inch x 2 inch by 0.125 inch strips of kiln dried fir, each layer consisting of 4 pieces. The crib is soaked with heptane, ignited, and allowed to burn for five minutes. The agent is then discharged onto the fire, rapid (< 2 seconds) extinguishment can be achieved; a total of 25 grams of agent is discharged. Immediately after extinguishment, the wood crib is cold to the touch, demonstrating the efficient suppression afforded by the agent.

Example 13: CF3CHFCF20CF3 Cup Burner [0077] Extinguishing concentrations of the hydrofluoroether CF3CHFCF20CF3 can be determined using a cup burner apparatus, as described in M. Robin and Thomas F. Rowland, "Development of a Standard Cup Burner Apparatus: NFPA and ISO Standard Methods, 1999 Halon Options Technical Working Conference, Apr.

27-29,1999, Albuquerque, N. Mex.". The cup burner method is a standard method for determining extinguishing mixtures and has been adopted in both national and international fire suppression standards. For example, NFPA 2001 Standard on Clean Agent Fire Extinguishing Systems and ISO 14520-1: Gaseous Fire-Extinguishing Systems, both utilize the cup burner method.

[0078] A mixture of air and CF3CHFCF20CF3 is flowed through an 85 mm (ID) Pyrex chimney around a 28 mm (OD) fuel cup. A wire mesh screen and a 76 mm (3 inch) layer of 3 mm (OD) glass beads are employed in the diffuser unit to provide thorough mixing of air and CF3CHFCF2OCF3.

[0079] n-Heptane is gravity fed to a cup from a liquid fuel reservoir consisting of a 250 mL separatory funnel mounted on a laboratory jack, which can allow for an adjustable and constant liquid fuel level in the cup. The fuel is ignited with a propane mini-torch and the chimney is placed on the apparatus. The fuel level is then adjusted such that fuel is 1-2 mm from the ground inner edge of the cup. A 90 second preburn period is allowed, and a primary flow of air is initiated via a calibrated flow meter @ 20- 40 Li'min.

[0080] Primary and secondary air flows are monitored by calibrated flow meters (210,225, 230 and 240 tubes). The flows are maintained until the flames are extinguished. A constant primary flow (240 tube) between 20 to 40 L/min is maintained in all the tests. The secondary flow of air is passed through CF3CHFCF20CF3 contained in a 1150 ml steel mixing chamber equipped with a dip-tube. The secondary flow, containing air saturated with CF3CHFCF20CF3, exits the mixing chamber and is mixed with the primary air flow before entering the cup burner's diffuser unit.

[0081] Immediately following flame extinction, a sample of the gas stream at a point near the lip of the cup is collected through a length of plastic tubing attached to a three way valve and multifit gas syringe. The sample is then subjected to gas chromatographic analysis (G. C. ). G. C. calibration is performed by preparing standards samples in a 1 L Tedlaro (E. I. DuPont De Nemours and Co. Corp. , 1007 Market Street, Wilmington, Delaware) bag.

[0082] A summary of test parameters and results are shown below in Table 8.

TABLE 8 Extinguishment of n-heptane Flames with CF3CHFCF20CF3 Test Primary Airflow CF3CHFCF20CF3 (imin) % (v/v) 1 20. 6 4. 97 2 20. 6 5. 40 3 20. 6 5. 38 4 20. 6 5. 38 5 34. 2 4. 90 6 41.1 5.18 7 41.1 5.13 8 41.1. 5.37 9 41. 1 5. 40 10 41. 1 5. 36 Docket No. PC3-045 [0083] Additional objects, advantages, and other novel features of the invention will become apparent to those skilled in the art upon examination of the foregoing or may be learned with practice of the invention. The foregoing description of the embodiments of the invention has been presented for purposes of illustration and description. It is not intended to be exhaustive or to limit the invention to the precise form disclosed. Obvious modifications or variations are possible in the light of the above teachings. Embodiments were chosen and described to provide the best illustrations of the principals of the invention and their practical application, thereby enabling one of ordinary skill in the art to utilize the invention in various embodiments and with various modifications as are suited to the particular use contemplated. All such modifications and variations are within the scope of the invention as determined by the appended claims when interpreted in accordance with the breadth to which they are fairly, legally, and equitably entitled.




 
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